US4400499A - Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers - Google Patents

Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers Download PDF

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US4400499A
US4400499A US06/335,521 US33552181A US4400499A US 4400499 A US4400499 A US 4400499A US 33552181 A US33552181 A US 33552181A US 4400499 A US4400499 A US 4400499A
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integrated process
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Ismael Colon
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BP Corp North America Inc
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • aryl polyhalide monomers are then coupled by contacting the monomers with a catalyst mixture of a nickel compound and a ligand in the presence of a reducing metal, e.g., zinc, and an aprotic solvent, e.g., N,N-dimethylacetamide, under substantially anhydrous conditions to form a substantially linear high molecular weight thermoplastic polymer.
  • a reducing metal e.g., zinc
  • an aprotic solvent e.g., N,N-dimethylacetamide
  • This invention relates to an integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers derived from aryl polyhalide monomers. More particularly, the invention relates to the intermediate preparation of aryl polyhalide monomers in a liquid phase of an aprotic solvent and an azeotrope former wherein water is removed from the reaction mass as an azeotrope until substantially anhydrous conditions are attained.
  • the aryl polyhalide monomers are then coupled through carbon-to-carbon bonding by contacting the monomers with a catalyst mixture of a nickel compound and a ligand in the presence of a reducing metal and an aprotic solvent under substantially anhydrous conditions to form a substantially linear high molecular weight themoplastic polymer.
  • the substantially linear high molecular weight thermoplastic polymers prepared in accordance with the integrated process of the present invention are relatively inexpensive and also relatively simple to prepare. These polymers exhibit excellent strength and toughness properties as well as outstanding thermal, oxidative and chemical stability. They find wide utility in the production of shaped and molded articles where such properties are necessary and are highly desirable and also in the preparation of film and fiber products which have excellent mechanical properties.
  • an azeotrope former e.g., toluene
  • an aprotic solvent effectively removes water from an aryl polyhalide monomer reaction mixture until sufficient anhydrous conditions are attained for directly contacting the aryl polyhalide monomers with a catalyst mixture in the presence of a reducing metal and an aprotic solvent under substantially anhydrous conditions to form substantially linear high molecular weight thermoplastic polymers by carbon-to-carbon bond polymerization.
  • U.S. Pat. No. 4,263,466 describes a method of coupling aryl and heteroaryl mono chlorides in an aprotic solvent under an inert atmosphere by employing a catalyst mixture of nickel compound and a ligand in the presence of a reducing metal to form coupled products, e.g., biphenyl compounds.
  • U.S. Pat. No. 4,175,175 and U.S. Pat. No. 4,108,837 describe high molecular weight polyarylene polyethers which are the linear thermoplastic reaction products of an alkali metal double salt of a dihydric phenol, e.g., dipotassium salt of 2,2-bis(4-hydroxyphenyl)propane, and a dihalobenzenoid compound, e.g., 4,4'-dichlorophenylsulfone.
  • the polymers have a basic structure composed of recurring units having the formula
  • E is the residuum of the dihydric phenol and E' is the residuum of the dihalobenzenoid compound, both of which are valently bonded to the ether oxygen through aromatic carbon atoms.
  • the polymerization reaction is conducted in a liquid phase of a sulfoxide or sulfone organic solvent and an azeotrope former such as chlorobenzene, dichlorobenzene and xylene. Water is removed from the reaction as an azeotrope with the azeotrope former to avoid the reaction of water with the dihalobenzenoid compound which leads to the formation of phenolic species and only low molecular weight products are secured.
  • the reaction is carried out in the presence of [Ni(PPh 3 ) 2 Cl 2 ], triphenylphosphine and zinc powder at a temperature of 50° C. as described on page 4090.
  • Table II on page 4091 describes the homo coupling of various organic bromide compounds to biphenyl.
  • the reference additionally states on page 4091 that the addition of iodide ions to the reaction mixture greatly accelerates the coupling reaction.
  • the present invention provides an integrated process for preparing a substantially linear high molecular weight thermoplastic polymer derived from an aryl polyhalide monomer which comprises:
  • aryl polyhalide monomers by contacting said monomers with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof and in a liquid phase of an aprotic solvent under substantially anhydrous conditions for a time and at a temperature sufficient to form a substantially linear high molecular weight thermoplastic polymer, wherein the catalyst mixture comprises an anhydrous nickel compound and at least one ligand selected from the group consisting of a triarylphosphine having from about 6 to about 14 carbon atoms in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and from about 5 to about 30 carbon atoms and wherein the ratio of gram atoms of nickel per mole of aryl polyhalide monomer is from about 0.001 to about 0.1, the amount of ligand is from about 1 to about 50 moles per gram atom of nickel and the amount of reducing metal is at least about 1 mole or reducing metal per
  • the process of the instant invention is appropriately termed an integrated process to describe the uniting of the monomer reaction, i.e., the preparation of aryl polyhalide monomers, with the polymerization reaction, i.e., the preparation of high molecular weight polymers, under substantially anhydrous conditions, thereby eliminating previously required additional procedural step such as isolation and purification of the aryl polyhalide monomers and the resulting problems of handling and expense attributable to these steps.
  • the present invention also provides substantially linear high molecular weight thermoplastic polymers having recurring units of the general formula:
  • E is the residuum of a dihydric phenol compound and E' is the residuum of a dihalobenzenoid compound and wherein the E residuum is valently bonded to ether oxygens through aromatic carbon atoms and the E' residua are valently bonded to each of an aromatic carbon atom and an ether oxygen through an aromatic carbon atom.
  • the present invention further provides substantially linear high molecular weight thermoplastic polymers having recurring units of the general formula:
  • E is the residuum of a phenol compound and E' is the residuum of a dihalobenzenoid compound and wherein the E residuum and E' residuum are valently bonded to each of an aromatic carbon atom and an ether oxygen through an aromatic carbon atom.
  • the catalyst mixture described in (iv) above and the alkali metal salt of a phenol compound described in (i) above can be formed in situ in the presence of the aryl polyhalide monomer solution described in (ii) above.
  • the aryl polyhalide monomer solution can also be added to the catalyst mixture either continuously, incrementally or all at once so as to achieve the polymerization reaction.
  • the reaction can be readily conducted in batch, semi-continuous or continuous operation by the proper selection or adjustment of addition rate, reaction rate and temperature as is obvious to those skilled in the art from the present invention.
  • the integrated process of this invention proceeds in the liquid phase of an aprotic solvent at elevated temperatures as hereinafter more fully set forth.
  • the preferred aprotic solvents include dipolar solvent, such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, sulfolane and the like.
  • these aprotic solvents can be mixed with lower polarity inert solvents, such as saturated aliphatic hydrocarbons, including pentanes, hexanes, dodecanes, and the like; aromatic hydrocarbons, such as benzene, toluene, xylenes and the like; saturated aliphatic and cycloaliphatic ethers, such as diethyl ether, diglyme, tetrahydrofuran and the like.
  • N,N-dimethylacetamide is the most preferred aprotic solvent and toluene is the most preferred lower polarity inert solvent for use in the integrated process of this invention.
  • the same solvent can be employed in each procedural step of the integrated process of this invention, i.e., formation of the alkali metal salt of a phenol compound, formation of the aryl polyhalide monomers (monomer reaction) and formation of the substantially linear high molecular weight thermoplastic polymers (polymerization).
  • the solvent be maintained substantially anhydrous before and during the reaction. While amounts of water up to about 0.01 percent by weight can be tolerated, amounts of water substantially greater than this are desirably avoided as the reaction of water with the aryl polyhalide monomers in the presence of a nickel catalyst leads to reduction and only low molecular weight products are secured. The reaction of water with the catalyst mixture also leads to deactivation of the active catalyst.
  • the integrated system In order to secure the production of high molecular weight substantially linear thermoplastic polymers, the integrated system should be substantially anhydrous, and preferably with less than 0.01 percent by weight water in the reaction mixture.
  • the water content can be as high as 0.5 weight percent but the water content should preferably be reduced to at least about 0.01 weight percent before polymerization in the presence of a nickel catalyst can be effected, i.e., (iv) above.
  • the phenol compound and an alkali metal carbonate or hydroxide are admixed in essentially stoichiometric amounts and normal precautions taken to remove all the water of neutralization preferably by distillation of a water-containing azeotrope from the aryl polyhalide monomer solution.
  • Toluene is the preferred azeotrope-forming organic liquid. Heating the alkali carbonate or hydroxide, phenol compound and small amounts of the azeotrope former to reflux for several hours while removing the azeotrope is the most desirable. However, it is obvious that any other technique for removing essentially all of the water can be equally satisfactory.
  • the azeotrope former can be one either miscible or immiscible with the major aprotic solvent of the integrated process. If it is not miscible it should be one which will not cause precipitation of the aryl polyhalide monomer or the high molecular weight polymer in the reaction mass. Heptane is such a solvent. When employed, it will merely remain inert and immiscible in the reaction mass. if the azeotrope former would cause precipitation of the polymer, it should be removed almost completely from the reaction mass before initiating polymerization.
  • azeotrope formers which are miscible with the major solvents and which also act as cosolvents for polymer during polymerization.
  • Toluene and xylene are azeotrope formers of this class.
  • the azeotrope former should be one boiling below the decomposition temperature of the major solvent and be perfectly stable and inert in the process, particularly inert to the alkali metal carbonate or hydroxide when the alkali metal salt of the phenol compound is prepared in situ in the presence of the inert diluent or azeotrope former.
  • the phenol compound employed in the integrated process of this invention is not narrowly critical. It can be, for instance, a mononuclear monohydric phenol compound having at least one halogen group preferably in a position para or meta to the hydroxyl group such as p-chlorophenol and m-chlorophenol.
  • the phenol compound can also be a mononuclear dihydric phenol such as, for example, hydroquinone.
  • the phenol compound can further be a polynuclear monohydric phenol such as: ##STR1## or a polynuclear dihydric phenol such as: the bis-(hydroxylphenyl)alkanes such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone (bisphenol S); and di(hydroxyphenyl)ethers such as bis-(4-hydroxyphenyl)ether.
  • a polynuclear monohydric phenol such as: ##STR1## or a polynuclear dihydric phenol such as: the bis-(hydroxylphenyl)alkanes such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone (bisphenol S); and di(hydroxyphenyl)ethers such
  • the preferred phenol compounds include 2,2-bis-(4-hydroxyphenyl)propane, bis-(4-hydroxyphenyl)sulfone, bis-(4-hydroxyphenyl)ether, hydroquinone and p-chlorophenol. It is possible tha the phenol compounds be substituted with other inert nuclear substituents such as alkyl, alkoxy and the like inert substituents. Polynuclear dihydric phenol compounds useful in the integrated process of this invention are further described in U.S. Pat. No. 4,175,175 and U.S. Pat. No. 4,108,837.
  • any of the alkali metal carbonates or hydroxides e.g., potassium carbonate or potassium hydroxide
  • any alkali metal salt of the phenol compound can be used as the reactant in the monomer reaction.
  • Potassium and cesium salts have been found to react consideralby faster than the sodium salts, but due to expense of the cesium salts, the potassium salts are preferred.
  • the alkali metal salt of the phenol compound can be single metal salt such as preferrably the potassium salt of p-chlorophenol or a double metal salt such as the dipotassium salt of 2,2-bis-(4-hydroxyphenyl)propane or the dipotassium salt of hydroquinone.
  • the alkali metal carbonate or hydroxide and the phenol compound are admixed in about stoichiometric amounts sufficient to form the alkali metal salt of the phenol compound.
  • the integrated process of the instant invention is not limited to phenate salts as nucleophiles. Other nucleophiles such as hydroxides, alkoxides, and sulfyl and nitrogen nucleophiles may also be employed in this process.
  • any dihalobenzenoid compound or mixture of dihalobenzenoid compounds can be employed in this invention which compound or compounds has the two halogens bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho and para to the halogen group.
  • the dihalobenzenoid compound can be either mononuclear where the halogens are attached to the same benzenoid ring or polynuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of the benzenoid nucleus.
  • any of the halogens may be the reactive halogen substituents on the benzenoid compounds. Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity an the chlorine compounds for their inexpensiveness.
  • the aryl polyhalide monomer produced should not contain terminal aryl fluoride groups since these groups are not coupled efficiently by the nickel catalyst, thus preventing the formation of high molecular weight polymers.
  • a wide variety of electron withdrawing groups can be employed as the activator group in these compounds. It should be, of course, inert to the reaction, but otherwise its structure is not critical. Preferred are the strong activating groups such as the sulfone group ##STR2## bonding two halogen substituted benzenoid nuclei as in the 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, although such other strong withdrawing groups hereinafter mentioned can also be used with equal ease.
  • the preferred activating groups can be basically either of two types:
  • the reaction time is inordinately long in order to secure the desired aryl polyhalide monomers.
  • the higher temperatuers i.e., above room temperature and generally about 100° C., are much more preferred for shorter processing times and for a more economical system. Most preferred are temperatures between about 120° C. to 160° C. Higher temperatures can of course be employed, if desired, provided that care is taken to prevent degradation or decomposition of the reactants, the monomer and the solvents employed.
  • the reaction time can vary from minutes to as long as several hours.
  • the monomer reaction between the alkali metal salt of the phenol compound and the dihalobenzenoid compound proceeds on a variable stoichiometric basis such that the desired aryl polyhalide monomer is formed.
  • Stoichiometry is not critical and the only requirement is that the stoichiometric amounts employed insure that the resulting aryl polyhalide monomers are halogen terminated, preferably chlorine terminated. By varying the stoichiometry, one can vary the aryl polyhalide monomer ultimately produced and its properties.
  • E is the residuum of the phenol compound
  • E' is the residuum of the dihalobenzenoid compound.
  • E defined as being the "residuum of the phenol compound” of course refers to the residue of the phenol compound after the removal of the aromatic hydroxyl group or groups. It is seen also that as used herein, the E' term defined as being the "residuum of the dihalobenzenoid compound” refers to the aromatic or benzenoid residue of the compound after removal of one or both halogen atoms from the benzenoid nucleus.
  • Preferred aryl polyhalide monomers include among others the following: ##STR8## where X is halogen and R represents a member of the group consisting of hydrogen, lower alkyl, lower aryl and the halogen-substituted groups thereof; ##STR9## wherein X is halogen, preferably chlorine; ##STR10## wherein X is halogen, preferably chlorine; ##STR11## wherein X is halogen, preferably chlorine; and ##STR12## wherein X is halogen, preferably chlorine.
  • the sulfone group present in the above preferred aryl polyhalide monomers may be replaced with another activating group described hereinabove in regard to useful dihalobenzenoid compounds.
  • the aryl polyhalide monomer produced in (ii) described above may comprise a mixture of at least two aryl polyhalide monomers selected from the above described monomers.
  • the polymerization reaction or coupling of the aryl polyhalide monomers proceeds by directly contacting the monomers with a catalyst mixture in the presence of a reducing metal selected from the group consisting of zinc, magnesium and manganese or mixtures thereof.
  • the polymerization reaction is conducted in the presence of a liquid phase of an aprotic solvent under substantially anhydrous conditions for a time and at a temperature sufficient to form the substantially linear high molecular weight thermoplastic polymers.
  • the catalyst mixture comprises an anhydrous nickel compound and at least one ligand selected from the group consisting of a triarylphosphine having from about 6 to about 14 carbon atoms in each aryl moiety and an aromatic bidentate compound containiing at least one ring nitrogen atom and from about 5 to about 30 carbon atoms.
  • Suitable nickel compound are nickel (o) complexes and those reducible by organometallic and metal reducing agents.
  • These compounds include nickel halides, that is, the chlorides, bromides and iodides, nickel sulfates, nickel phosphates, nickel carbonates, nickel salts of organic acids having 1 to 18 carbons, such as, nickel formate, nickel acetate, and nickel organic complexes such as nickel acetylacetonate, dichloro- bis(triphenylphosphine)nickel (II) and the like; and nickel (O) compounds such as bis(1,5-cyclo-octadiene)nickel, tetrakis(triphenylphosphine)-nickel, and the like.
  • nickel halides that is, the chlorides, bromides and iodides, nickel sulfates, nickel phosphates, nickel carbonates, nickel salts of organic acids having 1 to 18 carbons, such as, nickel formate, nickel acetate, and nickel organic complexes such as nickel acetylacetonate, dichloro- bis(triphenylpho
  • the anion of the nickel compounds is unimportant and merely serves to provide nickel ion to the catalyst mixture, but it must not interfere with the reaction of the nickel compound with the ligand.
  • the preferred anions are the halides.
  • Suitable triarylphosphines include triphenylphosphine, triphenylphosphines containing alkyl or alkoxy substituents having up to about 8 carbon atoms, and unsubstituted or alkyl- and alkoxy-substituted trinaphthyl phosphines.
  • Suitable bidentate compounds include 2,2'-bipyridine, 1,10-phenanthroline, 1,8-naphthylpyridine, 2-methylaminopyridine, and the like.
  • the preferred catalyst mixture comprises nickel chloride, triphenylphosphine and 2,2'-bipyridine.
  • the preferred ratio of gram atoms of nickel per mole of aryl polyhalide monomer is about 0.001 to about 0.1, with the most preferred range being 0.005 to 0.02.
  • the ratio of triarylphosphine to nickel can range from 0 to about 100, preferably from about 10 to about 50 moles per gram atom of nickel.
  • the ratio of bidentate ligand to nickel can range from 0 to about 5, preferably from about 0.2 to about 2, moles of bidentate ligand to gram atom of nickel.
  • triarylphosphine and aromatic bidentate ligand wherein the ratio of triarylphosphine to nickel varies from about 10 to about 50, and the ratio of bidentate ligand to nickel varies from about 0.5 to about 2 moles per gram atom of nickel.
  • the preferred reducing metal for use in the polymerization reaction of aryl polyhalide monomers is zinc metal although magnesium and manganese metals can also be used. It is preferred that the metal be in finely divided form with an average sieve size of 20 or finer when measured on the U.S. sieve scale. Although the stoichiometric amount of reducing metal required in this polymerization or coupling reaction is about 1 mole of reducing metal per mole of aryl polyhalide monomer i.e., dihalide, it is preferred to use a 50 percent excess or greater.
  • nickel (o) ligand complex believed to be the active catalyst can be formed in situ in the presence of an aryl polyhalide monomer solution, but the catalyst is preferably preformed in situ prior to the addition of the aryl polyhalide monomer solution.
  • a method for the determination of zero valent nickel is described by C. A. Tolman, J. Am. Chem. Soc. 92, 2956 (1970). The presence of the active catalyst in the integrated process of this invention is indicated by the characteristic brown to red-brown color.
  • the polymerization or coupling reaction can take place at temperatures of from about 0° C. to about 250° C., preferably from about 25° C. to about 120° C., and most preferably from about 40° C. to about 100° C. Pressure is not critical and so superatmospheric or subatmospheric pressures can be used as well as atmospheric pressure.
  • the reaction is preferably carried out in an inert atmosphere. Reaction time can vary from minutes to as long as several hours.
  • Inorganic salt promoters may be used with the triarylphosphines as ligands to reduce reaction times and/or temperatures.
  • Preferred inorganic salt promoters include alkali, alkaline earth, zinc, magnesium, manganese, and aluminum halides, or mixtures thereof. Iodides, chlorides and bromides are particularly preferred.
  • the amount of promoter when used can range from about 0.1 to about 1000 moles per gram atom of nickel with about 1 to about 100 moles of promoter being preferred. If desired one can also employ alkali, alkaline earth, zinc, magnesium, manganese, and aluminum sulfates or phosphates or mixtures thereof as promoters.
  • the substantially linear thermoplastic polymers are characterized by high molecular weights.
  • the polymers are composed of recurring units of the residuum of the aryl polyhalide monomers, i.e., the aryl polyhalide monomer residue after the removal of the terminal halogen atoms on the aromatic nucleii.
  • the substantially linear high molecular weight thermoplastic polymers may have recurring units of various structural combinations including among others the following:
  • E is the residuum of the phenol compound and E' is the residuum of the dihalobenzenoid compound described hereinabove and wherein the E residuum and the E' residuum may be valently bonded to ether oxygens through aromatic carbon atoms or valently bonded to each of an aromatic carbon atom and an ether oxygen through an aromatic carbon atom. It is noted that the recurring units are valently bonded through aromatic carbon atoms during the polymerization reaction.
  • Preferred substantially linear high molecular weight thermoplastic polymers include among others the following: ##STR13## wherein R represents a member of the group consisting of hydrogen, lower alkyl, lower aryl and the halogen substituted groups thereof; ##STR14##
  • the sulfone group present in the above preferred substantially linear high molecular weight thermoplastic polymers may be replaced with another activating group described hereinabove in regard to useful dihalobenzenoid compounds.
  • the substantially linear high molecular weight thermoplastic polymers can include such compounds as polycarbonates, polysulfones, polyethersulfones, polyesters, polyarylates, polyurethanes, polyetherimides, polyimides and the like.
  • the substantially linear thermoplastic polymers are characterized by high molecular weights.
  • the molecular weight of these polymers is indicated by reduced viscosity in indicated solvents.
  • the viscosity of a resin solution bears a direct relationship to the weight average molecular size of the polymer chains, and is the most important single property that can be used to characterize the degree of polymerization.
  • the reduced viscosity assigned to the polymer masses of the present invention is therefore to be understood as significant in reflecting molecular size rather than consideration concerning the viscosity per se.
  • Most of these polymers have indicated ready solubility in N-methylpyrrolidinone, chloroform, or tetrachloroethane or other similar solvent. In all instances, the reduced viscosity above about 0.35 is an indication of a tough, strong fiber- or film-forming polymer with those having a reduced viscosity about 0.4 being most preferred.
  • Reduced viscosity as used herein was determined by dissolving a 0.2 gram sample of thermoplastic polymer in the indicated solvent, i.e., N-methylpyrrolidinone, contained in a 100 ml. volumetric flask so that the resultant solution measured exactly 100 ml at 25° C. in a constant temperature bath.
  • the viscosity of 3 ml. of the solution which had been filtered through a sintered glass funnel was determined in an Ostwald or similar type viscometer at 25° C. Reduced viscosity values were obtained from the equation: ##EQU1## wherein: t o is the efflux time of the pure solvent
  • C is the concentration of the polymer solution expressed in terms of grams of polymer per 100 ml. of solution.
  • Part B Preparation of Substantially Linear Thermoplastic Polymer
  • Examples 1 through 16 illustrate the preparation of substantially linear high molecular weight thermoplastic polymers derived from aryl polyhalide monomers. Substantially higher reduced viscosities of the polymers are obtained by employing the post azeotrope step in the preparation of the aryl polyhalide monomer (compare Example 5 employing no past azeotrope step and having a reduced viscosity of 0.18 with Example 6 employing a post azeotrope step and having a reduced viscosity of 0.78). When the catalyst mixture contains nickel chloride in an amount of 0.08 grams, triphenylphosphine should be present in the catalyst mixture in an amount of 9.0 grams.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
US06/335,521 1981-12-29 1981-12-29 Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers Expired - Fee Related US4400499A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US06/335,521 US4400499A (en) 1981-12-29 1981-12-29 Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers
CA000416348A CA1205599A (en) 1981-12-29 1982-11-25 Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers
JP57223139A JPS58118826A (ja) 1981-12-29 1982-12-21 多ハロゲン化アリ−ル単量体から実質的に線状の高分子量熱可塑性重合体を製造する一貫方法
AT82112078T ATE27292T1 (de) 1981-12-29 1982-12-28 Integriertes verfahren zur herstellung von im wesentlichen linearen hochmolekularen thermoplastischen polymeren aus polyhalogenaryl- monomeren.
DE8282112078T DE3276369D1 (en) 1981-12-29 1982-12-28 Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers
EP82112078A EP0085185B1 (en) 1981-12-29 1982-12-28 Integrated process for the preparation of substantially linear high molecular weight thermoplastic polymers from aryl polyhalide monomers

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US4489181A (en) * 1983-11-07 1984-12-18 Fox Daniel W Thermoplastic polycarbonate-polysulfone carbonate molding compositions
US4503168A (en) * 1983-05-25 1985-03-05 Union Carbide Corporation Cookware made from polyarylethersulfone
US5051495A (en) * 1987-05-18 1991-09-24 Imperial Chemical Industries Plc Production and/or handling of aryl polyethers and thioethers polymers
US5102971A (en) * 1988-06-25 1992-04-07 Bayer Aktiengesellschaft Soluble polyaromatic compounds
US5227457A (en) * 1988-02-17 1993-07-13 Maxdem Incorporated Rigid-rod polymers
US5521258A (en) * 1994-11-14 1996-05-28 General Electric Company Autoclave resistant blends of poly(ester-carbonate) and polyetherimide resins
US5532374A (en) * 1995-06-06 1996-07-02 Hitachi Chemical Company, Ltd. Method of preparation of bis-quinolines
US5565543A (en) * 1988-02-17 1996-10-15 Maxdem Incorporated Rigid-rod polymers
US5646231A (en) * 1988-02-17 1997-07-08 Maxdem, Incorporated Rigid-rod polymers
US5654392A (en) * 1988-02-17 1997-08-05 Maxdem Incorporated Rigid-rod polymers
US5668245A (en) * 1995-11-02 1997-09-16 Maxdem Incorporated Polymers with heterocyclic side groups
US5886130A (en) * 1995-11-02 1999-03-23 Maxdem Incorporated Polyphenylene co-polymers
US20050137378A1 (en) * 2003-12-17 2005-06-23 Hedges Winston L. Method for making amine-terminated polyarylene polyethers
CN100341922C (zh) * 1998-04-21 2007-10-10 住友化学株式会社 含芴聚合物及由其制成的场致发光器件
US20080090992A1 (en) * 2006-10-12 2008-04-17 Dolbier William R Novel methods for producing thermoplastic fluoropolymers
US9353220B2 (en) 2013-08-13 2016-05-31 Fresenius Medical Care Holdings, Inc. Process for making polyarylethers and use in membrane preparation

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Cited By (28)

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Publication number Priority date Publication date Assignee Title
US4503168A (en) * 1983-05-25 1985-03-05 Union Carbide Corporation Cookware made from polyarylethersulfone
US4489181A (en) * 1983-11-07 1984-12-18 Fox Daniel W Thermoplastic polycarbonate-polysulfone carbonate molding compositions
US5051495A (en) * 1987-05-18 1991-09-24 Imperial Chemical Industries Plc Production and/or handling of aryl polyethers and thioethers polymers
US5731400A (en) * 1988-02-17 1998-03-24 Maxdem Incorporated Rigid-rod polymers
US5760131A (en) * 1988-02-17 1998-06-02 Maxdem Incorporated Rigid-rod polymers
US6087467A (en) * 1988-02-17 2000-07-11 Maxdem Incorporated Rigid-rod polymers
US5976437A (en) * 1988-02-17 1999-11-02 Maxdem Incorporated Rigid-rod polymers
US5565543A (en) * 1988-02-17 1996-10-15 Maxdem Incorporated Rigid-rod polymers
US5646231A (en) * 1988-02-17 1997-07-08 Maxdem, Incorporated Rigid-rod polymers
US5646232A (en) * 1988-02-17 1997-07-08 Maxdem Incorporated Rigid-rod polymers
US5654392A (en) * 1988-02-17 1997-08-05 Maxdem Incorporated Rigid-rod polymers
US5659005A (en) * 1988-02-17 1997-08-19 Maxdem Incorporated Rigid-rod polymers
US5789521A (en) * 1988-02-17 1998-08-04 Maxdem Incorporated Rigid-rod polymers
US5721335A (en) * 1988-02-17 1998-02-24 Maxdem Incorporated Rigid-rod polymers
US5227457A (en) * 1988-02-17 1993-07-13 Maxdem Incorporated Rigid-rod polymers
US5756581A (en) * 1988-02-17 1998-05-26 Maxdem Incorporated Rigid-rod polymers
US5102971A (en) * 1988-06-25 1992-04-07 Bayer Aktiengesellschaft Soluble polyaromatic compounds
US5521258A (en) * 1994-11-14 1996-05-28 General Electric Company Autoclave resistant blends of poly(ester-carbonate) and polyetherimide resins
US5532374A (en) * 1995-06-06 1996-07-02 Hitachi Chemical Company, Ltd. Method of preparation of bis-quinolines
US5668245A (en) * 1995-11-02 1997-09-16 Maxdem Incorporated Polymers with heterocyclic side groups
US5886130A (en) * 1995-11-02 1999-03-23 Maxdem Incorporated Polyphenylene co-polymers
CN100341922C (zh) * 1998-04-21 2007-10-10 住友化学株式会社 含芴聚合物及由其制成的场致发光器件
CN101058672B (zh) * 1998-04-21 2012-07-04 住友化学株式会社 一种组合物及由其制成的场致发光器件
US20050137378A1 (en) * 2003-12-17 2005-06-23 Hedges Winston L. Method for making amine-terminated polyarylene polyethers
US6992165B2 (en) 2003-12-17 2006-01-31 Hexcel Corporation Method for making amine-terminated polyarylene polyethers
US20080090992A1 (en) * 2006-10-12 2008-04-17 Dolbier William R Novel methods for producing thermoplastic fluoropolymers
US7544765B2 (en) 2006-10-12 2009-06-09 University Of Florida Research Foundation, Inc. Methods for producing thermoplastic fluoropolymers
US9353220B2 (en) 2013-08-13 2016-05-31 Fresenius Medical Care Holdings, Inc. Process for making polyarylethers and use in membrane preparation

Also Published As

Publication number Publication date
EP0085185B1 (en) 1987-05-20
EP0085185A1 (en) 1983-08-10
JPS6121966B2 (enrdf_load_stackoverflow) 1986-05-29
ATE27292T1 (de) 1987-06-15
DE3276369D1 (en) 1987-06-25
CA1205599A (en) 1986-06-03
JPS58118826A (ja) 1983-07-15

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